Flame Retardant Exposure in Vehicles Is Influenced by Use in Seat Foam and Temperature.

Flame retardants (FRs) are added to vehicles to meet flammability standards, such as US Federal Motor Vehicle Safety Standard FMVSS 302. However, an understanding of which FRs are being used, sources in the vehicle, and implications for human exposure is lacking. US participants (n = 101) owning a vehicle of model year 2015 or newer hung a silicone passive sampler on their rearview mirror for 7 days. Fifty-one of 101 participants collected a foam sample from a vehicle seat. Organophosphate esters (OPEs) were the most frequently detected FR class in the passive samplers. Among these, tris(1-chloro-isopropyl) phosphate (TCIPP) had a 99% detection frequency and was measured at levels ranging from 0.2 to 11,600 ng/g of sampler. TCIPP was also the dominant FR detected in the vehicle seat foam. Sampler FR concentrations were significantly correlated with average ambient temperature and were 2-5 times higher in the summer compared to winter. The presence of TCIPP in foam resulted in ∼4 times higher median air sampler concentrations in winter and ∼9 times higher in summer. These results suggest that FRs used in vehicle interiors, such as in seat foam, are a source of OPE exposure, which is increased in warmer temperatures.

Characterizing firefighter's exposure to over 130 SVOCs using silicone wristbands: A pilot study comparing on-duty and off-duty exposures.

Firefighters are occupationally exposed to an array of hazardous chemicals, and these exposures have been linked to the higher rates of some cancer in firefighters. However, additional research that characterizes firefighters' exposure is needed to fully elucidate the impacts on health risks. In this pilot study, we used silicone wristbands to quantify off-duty and on-duty chemical exposures experienced by 20 firefighters in Durham, North Carolina. By using each firefighter's off-duty wristband to represent individual baseline exposures, we assessed occupation-related exposures (i.e. on-duty exposures). We also investigated the influence of responding to a fire event while on-duty. In total, 134 chemicals were quantified using both GC-MS and LC-MS/MS targeted methods. Seventy-one chemicals were detected in at least 50% of all silicone wristbands, including 7 PFAS, which to our knowledge, have not been reported in wristbands previously. Of these, phthalates were generally measured at the highest concentrations, followed by brominated flame retardants (BFRs) and organophosphate esters (OPEs). PFAS were measured at lower concentrations overall, but firefighter PFOS exposures while on-duty and responding to fires were 2.5 times higher than off-duty exposures. Exposure to polycyclic aromatic hydrocarbons (PAH), BFRs, and some OPEs were occupationally associated, with firefighters experiencing 0.5 to 8.5 times higher exposure while on-duty as compared to off-duty. PAH exposures were also higher for firefighters who respond to a fire than those who did not while on-duty. Additional research with a larger population of firefighters that builds upon this pilot investigation may further pinpoint exposure sources that may contribute to firefighters' risk for cancer, such as those from firefighter gear or directly from fires. This research demonstrates the utility of using silicone wristbands to quantify occupational exposure in firefighters and the ability to disentangle exposures that may be specific to fire events as opposed to other sources that firefighters might experience.

Characterization of Per- and Polyfluorinated Alkyl Substances Present in Commercial Anti-fog Products and Their In Vitro Adipogenic Activity.

Anti-fog sprays and solutions are used on eyeglasses to minimize the condensation of water vapor, particularly while wearing a mask. Given their water-repellent properties, we sought to characterize per- and polyfluorinated alkyl substance (PFAS) compounds in four anti-fog spray products, five anti-fog cloth products, and two commercial fluorosurfactant formulations suspected to be used in preparing anti-fog products. Fluorotelomer alcohols (FTOHs) and fluorotelomer ethoxylates (FTEOs) were detected in all products and formulations. While 6:2 FTOH and the 6:2 FTEO polymeric series were predominant, one anti-fog cloth and one formulation contained 8:2, 10:2, 12:2, 14:2, and 16:2 FTOH and FTEO polymeric series. PFAS concentrations varied in samples and were detected at levels up to 25,000 µg/mL in anti-fog sprays and 185,000 µg (g cloth)-1 in anti-fog cloth products. The total organic fluorine (TOF) measurements of anti-fog products ranged from 190 to 20,700 µg/mL in sprays and 44,200 to 131,500 µg (g cloth)-1 in cloths. Quantified FTOHs and FTEOs accounted for 1-99% of TOF mass. In addition, all four anti-fog sprays and both commercial formulations exhibited significant cytotoxicity and adipogenic activity (either triglyceride accumulation and/or pre-adipocyte proliferation) in murine 3T3-L1 cells. Results suggest that FTEOs are a significant contributor to the adipogenic activity exhibited by the anti-fog sprays. Altogether, these results suggest that FTEOs are present in commercial products at toxicologically relevant levels, and more research is needed to fully understand the health risks from using these PFAS-containing products.

Comparative Assessment of Pesticide Exposures in Domestic Dogs and Their Owners Using Silicone Passive Samplers and Biomonitoring.

Pesticides are used extensively in residential settings for lawn maintenance and in homes to control household pests including application directly on pets to deter fleas and ticks. Pesticides are commonly detected in the home environment where people and pets can be subject to chronic exposure. Due to increased interest in using companion animals as sentinels for human environmental health studies, we conducted a comparative pesticide exposure assessment in 30 people and their pet dogs to determine how well silicone wristbands and silicone dog tags can predict urinary pesticide biomarkers of exposure. Using targeted gas chromatography-mass spectrometry analyses, we quantified eight pesticides in silicone samplers and used a suspect screening approach for additional pesticides. Urine samples were analyzed for 15 pesticide metabolite biomarkers. Several pesticides were detected in >70% of silicone samplers including permethrin, N,N-diethyl-meta-toluamide (DEET), and chlorpyrifos. Significant and positive correlations were observed between silicone sampler levels of permethrin and DEET with their corresponding urinary metabolites (rs = 0.50-0.96, p < 0.05) in both species. Significantly higher levels of fipronil were observed in silicone samplers from participants who reported using flea and tick products containing fipronil on their dog. This study suggests that people and their dogs have similar pesticide exposures in a home environment.

Monitoring Human Exposure to Organophosphate Esters: Comparing Silicone Wristbands with Spot Urine Samples as Predictors of Internal Dose.

Silicone wristbands present a noninvasive exposure assessment tool and an alternative to traditional biomonitoring; however, questions about their utility remain as validation studies are limited. We sought to determine if wristbands provide quantitative estimates of internal organophosphate ester (OPE) exposure. We evaluated internal dose by measuring metabolite masses excreted in 24-hour urine samples collected over five days among ten adults. We compared internal dose to OPE concentrations in paired wristbands worn during collection and, as a comparison, evaluated metabolite levels in spot urine samples. Three of six OPE metabolites evaluated were detected in >98% of urine samples, and 24 of 34 assessed OPEs were detected in at least one wristband. OPE uptake in wristbands was linear over time (range=0.54-61.8 ng/g/day). OPE concentrations in spot urine and wristbands were not correlated with total diphenyl phosphate (DPHP) excreted in urine, which may be due to the range of possible DPHP parent compounds or dietary exposure. However, for tris-(1,3-dichloro-2-propyl)phosphate (TDCIPP) and tris-(2-chloroisopropyl)phosphate (TCIPP), wristbands and spot urine samples were both moderately to strongly correlated with internal dose (all rs>0.56 and p<0.1), suggesting both perform well as integrated exposure estimates. Given the potential advantages of silicone wristbands, further studies investigating additional compounds are warranted.

Thyroid Receptor Antagonism of Chemicals Extracted from Personal Silicone Wristbands within a Papillary Thyroid Cancer Pilot Study.

Research suggests that thyroid cancer incidence rates are increasing, and environmental exposures have been postulated to be playing a role. To explore this possibility, we conducted a pilot study to investigate the thyroid disrupting bioactivity of chemical mixtures isolated from personal silicone wristband samplers within a thyroid cancer cohort. Specifically, we evaluated TRß antagonism of chemical mixtures extracted from wristbands (n = 72) worn by adults in central North Carolina participating in a case-control study on papillary thyroid cancer. Sections of wristbands were solvent-extracted and analyzed via mass spectrometry to quantify a suite of semivolatile chemicals. A second extract from each wristband was used in a bioassay to quantify TRß antagonism in human embryonic kidney cells (HEK293/17) at concentrations ranging from 0.1 to 10% of the original extract (by volume). Approximately 70% of the sample extracts tested at a 1% extract concentration exhibited significant TRß antagonism, with a mean of 30% and a range of 0-100%. Inhibited cell viability was noted in >20% of samples that were tested at 5 and 10% concentrations. Antagonism was positively associated with wristband concentrations of several phthalates, organophosphate esters, and brominated flame retardants. These results suggest that personal passive samplers may be useful in evaluating the bioactivities of mixtures that people contact on a daily basis. We also report tentative associations between thyroid receptor antagonism, chemical concentrations, and papillary thyroid cancer case status. Future research utilizing larger sample sizes, prospective data collection, and measurement of serum thyroid hormone levels (which were not possible in this study) should be utilized to more comprehensively evaluate these associations.

In Vitro Metabolism of Isopropylated and tert-Butylated Triarylphosphate Esters Using Human Liver Subcellular Fractions.

Isopropylated and tert-butylated triarylphosphate esters (ITPs and TBPPs, respectively) are plasticizers and flame retardants that are ubiquitous in indoor environments; however, no studies to date have characterized their metabolism. Using human liver subcellular S9 fractions, phase I and II in vitro metabolism of triphenyl phosphate (TPHP), 4-tert-butylphenyl diphenyl phosphate (4tBPDPP), 2-isopropylphenyl diphenyl phosphate (2IPPDPP), and 4-isopropylphenyl diphenyl phosphate (4IPPDPP) was investigated at 1 and 10 µM doses. Parent depletion and the formation of known or suspected metabolites (e.g., likely hydrolysis or hydroxylated products), including diphenyl phosphate (DPHP), hydroxyl-triphenyl phosphate (OH-TPHP), isopropylphenyl phenyl phosphate (ip-PPP), and tert-butylphenyl phenyl phosphate (tb-PPP), were monitored and quantified via GC/MS or LC-MS/MS. tb-PPP and its conjugates were identified as the major in vitro metabolites of 4tBPDPP and accounted for 71% and 49%, respectively, of the parent molecule that was metabolized during the incubation. While the mass balance between parents and metabolites was conserved for TPHP and 4tBPDPP, approximately 20% of the initial parent mass was unaccounted for after quantifying suspected metabolites of 2IPPDPP and 4IPPDPP that had authentic standards available. Two novel ITP metabolites, mono-isopropenylphenyl diphenyl phosphate and hydroxy-isopropylphenyl diphenyl phosphate, were tentatively identified by high-resolution mass spectrometry and screened for in recently collected human urine where mono-isopropenylphenyl diphenyl phosphate was detected in one of nine samples analyzed. This study provides insight into the biological fate of ITP and TBPP isomers in human tissues and is useful in identifying appropriate biomarkers of exposure to monitor, particularly in support of epidemiological studies.

Determination of PCB fluxes from Indiana Harbor and Ship Canal using dual-deployed air and water passive samplers.

We have developed a method for measuring fluxes of PCBs from natural waters using air and water passive samplers deployed simultaneously in the Indiana Harbor and Ship Canal (IHSC). Net volatilization of Æ©PCBs was determined for 2017, and ranged from 1.4 to 2.8 µg m-2 d-1, with a median of 2.0 µg m-2 d-1. We confirm earlier findings that the IHSC experiences constant release of gas-phase PCBs. Gas-phase and freely-dissolved water Æ©PCB samples median were 4.0 ng m-3 and 14 ng L-1, both exhibiting increasing concentrations over the year of study, and with a strong positive correlation between them (R2 = 0.93 for Æ©PCBs). The relative concentrations of individual PCB congeners were very similar between air and water samples, and resemble Aroclor 1248, a mixture previously reported to contaminate the IHSC sediments. Monthly variability of the volatilization fluxes was primarily driven by the freely-dissolved water concentration changes (R2 = 0.87). Although different sampling methods were performed to estimate air-water fluxes between the month of August of 2006 and 2017, Æ©PCB net fluxes have decreased by more than 60%, suggesting that either dredging at IHSC from 2012 to 2017 or reduction of upstream sources have decreased the freely-dissolved water concentrations of PCBs, thus reducing the air-water net volatilization in IHSC. Finally, we have shown that this passive sampling approach represents a simple and cost-effective method to assess the air-water exchange of PCBs, increase analytical sensitivity, enable measurements over time, and reduce uncertainties related to unexpected episodic events.

Emissions of Tetrachlorobiphenyls (PCBs 47, 51, and 68) from Polymer Resin on Kitchen Cabinets as a Non-Aroclor Source to Residential Air.

Both Aroclor and non-Aroclor sources of airborne polychlorinated biphenyls (PCBs) were found in residential homes. We deployed passive air samplers at 16 residences and found PCB-47, PCB-51, and PCB-68 to account for up to 50% of measured indoor ΣPCBs (2700 pg m-3). Although PCB-47 and PCB-51 are neurotoxins present in Aroclor mixtures (<2.5 and <0.3 wt %, respectively), we found them at much higher levels than expected for any Aroclor source. PCB-68 is not present in Aroclor mixtures. Another non-Aroclor congener, PCB-11, a byproduct of pigment manufacturing, was found inside and outside of every household and was frequently the predominate congener. We conducted direct measurements of surface emissions and identified finished cabinetry to be a major source of PCB-47, PCB-51, and PCB-68. We hypothesize that these congeners are inadvertent byproducts of polymer sealant manufacturing and produced from the decomposition of 2,4-dichlorobenzoyl peroxide used as an initiator in free-radical polymerization of polyester resins. The presence of these three compounds in polymer products, such as silicone, has been widely noted, but to our knowledge they have never been shown to be a significant environmental source of PCBs.

Effects of room airflow on accurate determination of PUF-PAS sampling rates in the indoor environment.

Accurate and precise interpretation of concentrations from polyurethane passive samplers (PUF-PAS) is important as more studies show elevated concentrations of PCBs and other semivolatile air toxics in indoor air of schools and homes. If sufficiently reliable, these samplers may be used to identify local sources and human health risks. Here we report indoor air sampling rates (Rs) for polychlorinated biphenyl congeners (PCBs) predicted for a frequently used double-dome and a half-dome PUF-PAS design. Both our experimentally calibrated (1.10 ± 0.23 m3 d-1) and modeled (1.08 ± 0.04 m3 d-1) Rs for the double-dome samplers compare well with literature reports for similar rooms. We determined that variability of wind speeds throughout the room significantly (P < 0.001) effected uptake rates. We examined this effect using computational fluid dynamics modeling and 3-D sonic anemometer measurements and found the airflow dynamics to have a significant but small impact on the precision of calculated airborne concentrations. The PUF-PAS concentration measurements were within 27% and 10% of the active sampling concentration measurements for the double-dome and half-dome designs, respectively. While the half-dome samplers produced more consistent concentration measurements, we find both designs to perform well indoors.

Calibration and evaluation of PUF-PAS sampling rates across the Global Atmospheric Passive Sampling (GAPS) network.

Passive air samplers equipped with polyurethane foam (PUF-PAS) are frequently used to measure persistent organic pollutants (POPs) in ambient air. Here we present and evaluate a method to determine sampling rates (RS), and the effective sampling volume (Veff), for gas-phase chemical compounds captured by a PUF-PAS sampler deployed anywhere in the world. The method uses a mathematical model that requires only publicly available hourly meteorological data, physical-chemical properties of the target compound, and the deployment dates. The predicted RS is calibrated from sampling rates determined from 5 depuration compounds (13C PCB-9, 13C PCB-15, 13C PCB-32, PCB-30, and d6-γ-HCH) injected in 82 samples from 24 sites deployed by the Global Atmospheric Passive Sampling (GAPS) network around the world. The dimensionless fitting parameter, gamma, was found to be constant at 0.267 when implementing the Integrated Surface Database (ISD) weather observations and 0.315 using the Modern Era Retrospective-Analysis for Research and Applications (MERRA) weather dataset. The model provided acceptable agreement between modelled and depuration determined sampling rates, with 13C PCB-9, 13C PCB-32, and d6-γ-HCH having mean percent bias near zero (±6%) for both weather datasets (ISD and MERRA). The model provides inexpensive and reliable PUF-PAS gas-phase RS and Veff when depuration compounds produce unusual or suspect results and for sites where the use of depuration compounds is impractical, such as sites experiencing low average wind speeds, very cold temperatures, or remote locations.

Airborne PCBs and OH-PCBs Inside and Outside Urban and Rural U.S. Schools.

PCBs appear in school air because many school buildings were built when PCBs were still intentionally added to building materials and because PCBs are also present through inadvertent production in modern pigment. This is of concern because children are especially vulnerable to the toxic effects of PCBs. Here we report indoor and outdoor air concentrations of PCBs and OH-PCBs from two rural schools and four urban schools, the latter near a PCB-contaminated waterway of Lake Michigan in the United States. Samples (n = 108) were collected as in/out pairs using polyurethane foam passive air samplers (PUF-PAS) from January 2012 to November 2015. Samples were analyzed using GC/MS-MS for all 209 PCBs and 72 OH-PCBs. Concentrations inside schools were 1-2 orders of magnitude higher than outdoors and ranged from 0.5 to 194 ng/m3 (PCBs) and from 4 to 665 pg/m3 (OH-PCBs). Congener profiles were similar within each sampling location across season but different between schools and indicated the sources as Aroclors from building materials and individual PCBs associated with modern pigment. This study is the first cohort-specific analysis to show that some children's PCB inhalation exposure may be equal to or higher than their exposure through diet.

Release of Airborne Polychlorinated Biphenyls from New Bedford Harbor Results in Elevated Concentrations in the Surrounding Air.

Qualitatively and quantitatively, we have demonstrated that airborne polychlorinated biphenyl (PCB) concentrations in the air surrounding New Bedford Harbor (NBH) are caused by its water PCB emissions. We measured airborne PCBs at 18 homes and businesses near NBH in 2015, with values ranging from 0.4 to 38 ng m-3, with a very strong Aroclor 1242/1016 signal that is most pronounced closest to the harbor and reproducible over three sampling rounds. Using U.S. Environmental Protection Agency (U.S. EPA) water PCB data from 2015 and local meteorology, we predicted gas-phase fluxes of PCBs from 160 to 1200 µg m-2 day-1. Fluxes were used as emissions for AERMOD, a widely applied U.S. EPA atmospheric dispersion model, to predict airborne PCB concentrations. The AERMOD predictions were within a factor of 2 of the field measurements. PCB emission from NBH (110 kg year-1, average 2015) is the largest reported source of airborne PCBs from natural waters in North America, and the source of high ambient air PCB concentrations in locations close to NBH. It is likely that NBH has been an important source of airborne PCBs since it was contaminated with Aroclors more than 60 years ago.

A Model Using Local Weather Data to Determine the Effective Sampling Volume for PCB Congeners Collected on Passive Air Samplers.

We have developed and evaluated a mathematical model to determine the effective sampling volumes (Veff) of PCBs and similar compounds captured using polyurethane foam passive air samplers (PUF-PAS). We account for the variability in wind speed, air temperature, and equilibrium partitioning over the course of the deployment of the samplers. The model, provided as an annotated Matlab script, predicts the Veff as a function of physical-chemical properties of each compound and meteorology from the closest Integrated Surface Database (ISD) data set obtained through NOAA's National Centers for Environmental Information (NCEI). The model was developed to be user-friendly, only requiring basic Matlab knowledge. To illustrate the effectiveness of the model, we evaluated three independent data sets of airborne PCBs simultaneously collected using passive and active samplers: at sites in Chicago, Lancaster, UK, and Toronto, Canada. The model provides Veff values comparable to those using depuration compounds and calibration against active samplers, yielding an average congener specific concentration method ratio (active/passive) of 1.1 ± 1.2. We applied the model to PUF-PAS samples collected in Chicago and show that previous methods can underestimate concentrations of PCBs by up to 40%, especially for long deployments, deployments conducted under warming conditions, and compounds with log Koa values less than 8.